Lignin dewatering process

ABSTRACT

A lignin plastics solids mass containing lignin solids and liquids with up to 85% liquids can be partially dewatered by heating the lignin plastics solids mass to above a critical temperature at which time the lignin plastics solids agglomerate into lower moisture granular solids with between about 45% to 55% liquids releasing excess liquid which can be easily removed from the solids. The process is particularly useful for lignin plastics solids removed from black liquor from paper mills, or for similar lignin plastics solids masses, which can contain up to 85% liquids and which need to be dried to form useful lignin solids, which can be used for example for fuel. The dewatering process can be combined with the process for separating the lignin from the black liquor to separate the dewatered lignin directly from the black liquor.

RELATED APPLICATIONS

This is a divisional of application Ser. No. 12/189,046, filed Aug. 8,2008, now U.S. Pat. No. 8,613,781, which claims the benefit of U.S.Provisional Patent Application No. 60/964,106, filed on Aug. 8, 2007,which is incorporated by reference herein in its entirety.

BACKGROUND OF THE INVENTION

Field: The invention relates to reduction of water content in ligneousmaterials with high moisture content, particularly ligneous materialssuch as lignin solids separated from paper industry spent pulpingliquor, such as spent waste alkaline digestion liquor known as “blackliquor.”

State of the Art: U.S. Pat. Nos. 5,635,024 and 6,632,327, herebyincorporated by reference, describe a process for recovering ligninsolids from spent, waste alkaline digestion liquors from the paperindustry. These liquors are generally referred to as “black liquors.”The recovery of lignin solids is accomplished by mixing into spentdigestion liquor a water soluble, surface active, polymeric, coagulantagent, and then acidifying the mixed liquor to a pH below 7 to separatethe lignin and other organic compounds, and to coagulate them as solidswhich tend to float to the surface of the residual liquid. Thecoagulated solids, which generally form a lignin plastics solids massare then separated from the residual liquid. These separated solids maycontain up to about 85 percent liquid, mostly water. To make beneficialuse of these solids, such as by combustion of the lignin solids as fuelfor generating electric power and steam, it is generally desired toreduce the water content of these solids. To use these lignin solids asfuel for generating electric power and steam, the water content shouldbe brought down to no more than about 30 percent water, and preferablyto the range of less than about 5 percent water to gain the bestpossible thermal efficiencies.

The separated lignin solids can be dried to reduce the moisture contentin commercial thermal treatment or drying equipment. However, thisequipment uses substantial amounts of energy to dry the lignin solids,and therefore reduces the overall thermal fuel efficiency. To reduceenergy consumed in drying, non-thermal means of reducing lignin solidsmoisture have been investigated such as mechanical separation of waterfrom the lignin by pressure. It has been shown that lignin moisturecontent can be reduced to about 65 percent by compression in a pressurecell device, and subsequently dried by thermal methods using acommercial system to further reduce the moisture. However, this processstill requires substantial drying energy. Even with the initialmechanical drying, however, the additional required drying by thermalmethods involves high energy consumption to an extent almost equivalentto the energy values derived from combustion of the dried lignin. Thesignificant energy needs in applying these past known techniques havediscouraged their acceptance.

In another application, high moisture content sewage sludge collectedfrom biological treatment, which sludge, in many respects, hasproperties similar to the lignin solids from black liquor, has beenpartially dewatered for combustion by filtration by the electrodewatering technique. Again, however, the significant energy needs inreducing the water content of the sludge have discouraged use of sludgeas an energy source. A simple and low energy cost method for processinglignin solids and similar materials such as sludge for water reductionis not known.

SUMMARY OF THE INVENTION

The inventor has discovered that lignin solids having high moisturecontent (up to about 85 percent water content) separated from blackliquor by the El-Shall process of U.S. Pat. Nos. 5,635,024 and6,632,327, can be induced to agglomerate into lower moisture granularlignin solids, having a moisture content typically in range of about 45to about 55 percent moisture, by heating the separated lignin mass toabove about 180° F. At a temperature in a range around about 180° F.,hereinafter referred to as the critical temperature, the lignin phaseundergoes transition. This critical temperature can vary according tothe characteristics and the source of lignin, such as whether extractedfrom wood or agricultural residues, and whether the lignin previouslyhad been subjected to digestion in a biological treatment facility. Thelignin used can be from any source, including one or more of paper orother processing facilities, discarded or waste biomass, wood,agriculture, etc. When the lignin mass being heated during the treatmentprocess reaches the critical temperature for separation, lignin solidsprecipitate as the mass is subsequently cooled, while released wateraccumulates as a supernatant.

The density difference between the water and the newly-formed solidsallows gravity to cause the lignin solids to settle below the aqueousphase. The principle part of the water released from the lignin mass isreadily decanted from the precipitated lignin solids after conductingthe described thermal treatment. The released water can be taken awayand recycled for biological treatment as in the usual application ofblack liquor treatment. Thus, for example, a quantity of lignin plasticmass of 1000 grams weight, typically containing 850 grams of water and150 grams of dry lignin solids, is caused by the inventive process todivide into a granular solids phase of approximately 300 grams ofmoisture infused solids—150 grams of water and 150 grams of drysolids—and a quantity of aqueous phase comprising about 700 grams. Thetreatment results in about 80 percent of water contained in the ligninplastic mass becoming supernatant for recycling, with only about 20percent of water remaining with the lignin solids. Optionally, theresidual water in the lignin solids can be reduced or eliminated furtherby means of thermal drying using commercially available equipment. Suchadditional drying can be in anticipation of, for example, using thelignin solids as a combustible fuel source to generate, e.g., power andsteam.

Other non-limiting examples of materials that may be likewise treatedinclude forestry debris and/or waste, forestry products including wood,and any other source of lignin.

The dewatering process of this invention can be combined with theEl-Shall black liquor-lignin separating process of the cited patents toprovide a separated and dewatered lignin product from the black liquorin substantially a single step. This can be done by providing twoprocess streams. One process stream can be dilute black liquor from thepaper mill mixed with polymer solution, which emerges fromdigestion/fiber separation at temperatures in range of about 200° F. toabout 300° F. The other process stream can be heated acidified dilution(clarified) liquor. If the two streams are at room temperature whencombined in the process, lignin separates as a high water contentplastic mass that then can be optionally dewatered by heating aspreviously disclosed. However, when the two heated liquid streams aremixed, lignin solids precipitate as the mixture cools. The lignin solidsrequire a finite reaction time for their transformation to the dewatered(consolidated) state. This can be implemented by discharging thecombined flow—after mixing—into a conical bottomed tank wherein thelignin begins precipitation as the mixture cools. It should be notedthat tanks or other storage containers can be utilized at this step inthe process, although conical bottomed tanks are exemplified herein. Bydischarging the combined flow into a tank, the necessary time isprovided for cooling and completing the lignin solids consolidationprocess and to separate the dewatered solids by gravity into the bottomof the tank. Dewatered lignin solids can be removed from the process bya physical separation means. A non-limiting example includes a screwconveyor or a similar suitable material handling device positioned toreceive the solids flowing from the bottom of the tank.

THE DRAWINGS

In the accompanying drawings, which show the best mode currentlycontemplated for carrying out the invention:

FIG. 1 shows three test tubes with test tube 1 containing a sample ofunprocessed high moisture lignin plastic mass from a black liquorseparation process, test tube 2 containing granulated wet solidsremaining after treatment, and test tube 3 containing the supernatantaqueous phase decanted after treatment;

FIG. 2 is a schematic flow diagram in block form of a black liquortreatment process incorporating the dewatering process; and

FIG. 3 is a schematic flow diagram of a second embodiment of a blackliquor treatment process incorporating the dewatering process.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENT

A method is presented herein wherein lignin plastic solids are at leastpartially dewatered in an energy effective manner. As such, the ligninplastic solids can be utilized as an effective fuel source. In oneaspect, the method includes heating lignin plastic solids to atemperature above a critical temperature and subsequently reducing thetemperature, thus causing the lignin plastic solids to agglomerate intolower moisture granular solids having a moisture content of less thanabout 60% and decanting at least a portion of the residual liquid toseparate the lower moisture solids from the residual liquid. In oneaspect, the lower moisture granular solids can have a moisture contentof less than about 50%, and in another aspect, the lower moisturegranular solids can have a moisture content of from about 45% to about55%. The critical temperature, as discussed further below, can, in oneaspect be greater than about 170° F., or even greater than about 180° F.In a specific embodiment, the critical temperature can range from about170° F. to about 200° F.

Similarly, a process for treating a substantially spent, alkaline andnon-sulphite digestion liquor obtained from a pulping plant of the papermaking industry, the digestion liquor containing lignin as a potentialprecipitant upon acidification of the digestion liquor and leavingsubstantially clarified residual liquid can include mixing into thespent digestion liquor a water soluble, surface active, polymericcoagulant agent. The process can further include acidifying the so mixedliquor to a pH below about 7 to precipitate the lignin and other organiccompounds and to coagulate them as solids which tend to float to thesurface of the residual liquid. In one specific embodiment, the so mixedliquor is acidified to a pH below about 3.5 and in another embodiment tobelow about 3. Further, the process can include heating the digestionliquor to a temperature above a critical temperature to cause the ligninto precipitate as lower moisture granular solids, and separating theprecipitated lower moisture granular solids from the residual liquid.

In one aspect, the surface active agent coactive with the polymericcoagulant agent is added to the spent digestion liquor prior to theacidification thereof so as to coact with the polymeric coagulant agentand thereby facilitate lignin separation. In another aspect, the surfaceactive agent is a water soluble surface active co-precipitant agent. Thedigestion liquor can be from a variety of sources. In one embodiment,the spent digestion liquor can be taken from a kraft process pulpingplant. In a further embodiment, the kraft process pulping plant caninclude a reducing recovery furnace and the spent digestion liquor takenfrom the plant is substantially only that produced in excess of what thefurnace is capable of handling. Alternatively, the spent digestionliquor can be taken from a soda process pulping plant. In a furtherembodiment, the spent digestion liquor can be taken from digestion ofany cellulosic biomass, such as agro waste or residue.

In one aspect, the coagulant agent is added to the spent digestionliquor before acidification of the liquor. In another aspect, thecoagulant agent is added to the spent digestion liquor duringacidification of the liquor. In still another embodiment, the spentdigestion liquor is diluted prior to treatment. The solids and theresidual liquors can be used as valuable products, in some aspects.

In a specific aspect, a process for treating a spent kraft alkalinedigestion liquor containing lignin and liquid can include mixing intothe spent kraft digestion liquor a water soluble, surface active,polymeric coagulant agent; acidifying the spent digestion liquor to a pHbelow about 3 to cause lignin and other dissolved organic compounds ofthe spent digestion liquor to coagulate as solids and float to thesurface of the spent digestion liquor; heating the digestion liquor andsolids to a temperature of greater than about 180° F. to form lowermoisture granular solids; and separating the lower moisture granularsolids and the residual liquid of the acidified spent digestion liquor.

In one aspect, the invention is a method for at least partiallydewatering a lignin plastic solids mass containing lignin solids and aliquid, by heating the lignin plastics solids mass to a criticaltemperature, which causes the lignin plastics solids to agglomerate intolower moisture content granular solids and releasing excess moisture inthe form of a liquid that can be decanted from the granular solids. Thisaspect of the invention can be advantageously applied to a ligninplastics solids mass containing lignin solids and a liquid, such as aportion of the black liquor which remains in the lignin plastics solidsmass when it is separated from the black liquor by the El-Shall methoddisclosed in cited U.S. Pat. Nos. 5,635,024 and 6,632,327. The ligninplastics solids mass can contain up to about 85 percent liquids, whichare mostly water. The lignin plastic solids mass is heated to atemperature above a critical temperature of greater than about 180° F.It should be noted that the term, “critical temperatures” as usedherein, is in relation to the specific method disclosed herein, and isnot necessarily associated with the “critical temperature” of classicchemistry. Herein, the term refers to the lowest temperature at whichlignin plastics solids mass converts to a supernatant liquid andgranular solids following elevation to the temperature followed bycooling. Additionally it is believed the critical temperature is that atwhich the lignin component of the mass or mixture melts. At thattemperature, the lignin plastics solids mass resulting from the citedEl-Shall method separates, where the lignin plastic solids agglomerateinto lower moisture granular solids having a moisture content of lessthan about 60%, releasing the excess liquor, mostly water, or otherliquid. At least a portion of the residual excess liquor or other liquidcan he decanted to provide a lower moisture lignin solid. It should benoted that the term, “high moisture content” as used herein can vary dueto the type of stream or materials, however, the term can generallyrefer to a moisture content of greater than about 85 percent waterand/or other liquid content. Thus, lignin plastic solids of highmoisture content produced from black liquor by the El-Shall process canbe induced to agglomerate the lignin plastics solids into lower moisturegranular solids by heating the plastic mass to above 180° F. Also, asused herein, the “lower moisture granular solids” refer to granularsolids having a lower moisture content than the lignin plastic solids orother process stream or material from which they are produced. Thedistinction between the granular solids and the lignin plastic solids orother process stream should be significant enough to at least partiallyproduce a visibly apparent physical separation. In one aspect, the lowermoisture granular solids can have a moisture content of from about 45percent to about 55 percent moisture. At the critical temperature, thelignin phase state undergoes transition. The transition temperature canvary according to characteristics and the source of the lignin (such aswhether extracted from wood or agricultural residues, and whether ligninpreviously had been subjected to digestion in a biological treatmentfacility). When the lignin mass being heated during the treatmentprocess reaches the critical temperature for separation, which isbelieved to be a temperature which liquidfies the lignin, lignin solidsprecipitate upon subsequent cooling, while released water or otherliquid remains as a supernatant. The supernatant can be an opticallyclean liquid, however, it typically is colored by dissolved matter.

Lignin granular solids settle by gravity to below the aqueous phase dueto the density differences between the granular solids and the water.The settling of the solids produces at least a partial separation ofgranular solids below a liquid supernatant. The supernatant, which istypically primarily composed of water, can then be readily decanted.Other forms of physical separation are also possible to separate thesupernatant from the granular solids. In one aspect, the released water,or supernatant can be recycled for biological treatment in the usualapplication of black liquor treatment as embodied in the processesemploying this invention.

Thus, for example, a quantity of lignin plastic mass of 1000 gramsweight typically containing 850 grams of water and 150 grams of drylignin solids is caused by the disclosed process to divide into agranular solids phase of approximately 300 grams of moisture infusedsolids—150 grams of water and 150 grams of dry solids—and a quantity ofaqueous phase comprising about 700 grams. The treatment results in about80 percent of water contained in the lignin plastic mass becomingsupernatant for recycling with only about 20 percent of water remainingwith the lignin solids.

In one aspect, at least some of the residual water in the granularsolids can be eliminated by further means such as by thermal dryingusing commercially available equipment in preparing lignin solids forfuel to generate power and steam. Optionally, ambient drying can beused. Preferably the drying temperature is below the criticaltemperature, and preferably below about 170° F.

FIG. 1 illustrates the results of the process described above by showingtest tubes with samples of lignin before and after treatment foreliminating the bulk of contained water from the original high moistureplastic mass, in FIG. 1, test tube 1 contains a sample of unprocessedhigh moisture lignin plastic mass from the black liquor separation. Testtube 2 contains granulated wet solids remaining after treatment, andtest tube 3 contains the supernatant aqueous phase decanted aftertreatment from the treated lignin mass. Thus, test tube 1 shows theoriginal high moisture plastic mass before the dewatering treatment.This mass contains about 85 percent moisture. Test tube 2 shows thegranulated solids which were precipitated out of the original mass intest tube 1 by heating to 180° F. Test tube 3 shows the excess moisturereleased from the lignin mass when the granulated solids shown in testtube 2 were formed.

Results of an example experiment are as follows: lignin plastic masssample weight in test tube 1 is 10.2 grams. Weight of wet granulatedsolids precipitated by the herein disclosed process is 2.9 grams in testtube 2. Weight of supernatant aqueous phase decanted from the treatmentinto test tube 3 is 7.3 grams by difference.

Additional experiments have been carried out on a small scale by batchtesting using beakers and microwave heating. Dilute black liquorobtained from a major paper company comprised of separate softwood kraftpulping liquor and hardwood kraft pulping liquor samples were used.Tests were also conducted using a soda chemical pulping liquor(non-kraft). All the experiments further confirmed efficacy of theprocess. Some of the experiments were planned toward gaining insight onhow the process would be operated continuously for use in a commercialinstallation.

FIG. 2 shows, in block diagram, a process for lignin separation fromblack liquor from a paper plant followed by lignin preparation (biomasspreparation) for use in a power plant. Black liquor flows on line 10from paper mill 12 to an anaerobic and aerobic digester 14 from whichthe black liquor flows, arrow 16, to lignin separator 18. Polymer hasbeen or is added to the black liquor and weak phosphoric acid is added,line 20, to the black liquor in the separator 18. This causes theseparation of the lignin mass from the black liquor to produce the wetlignin plastics mass which flows from the lignin separator 18 throughline 22 to the biomass preparation stage 24. Biomass preparation stage24 is broken out separately in the lower portion of FIG. 2 to show thelignin dewatering 26, which, as described above, involves heating thewet lignin plastics mass above the critical temperature (e.g., about180° F.) causing formation of the lignin granular solids and releasingliquid. These lower moisture content lignin granular solids are mixedwith other solids and are further filtered 28 and dried 30 and thenconveyed to a power plant 32. In this process, the lignin dewatering iscarried out as a separate step in the process.

In one aspect, a degree of lignin consolidation (essentially, ligninseparation and dewatering) can be induced by having the two contactingstreams separately raised to about or above the critical temperature,e.g., about 180° F. In a specific aspect, the two process streams can bedilute black liquor from a paper mill mixed with polymer solution, whichemerges from digestion/fiber separation at temperatures in range ofabout 200° F. to about 300° F. in a specific embodiment, the diluteblack liquor emerges at or around about 200° F. The second stream can,in one aspect, comprise or consist essentially of heated acidifieddilution (clarified) liquor. If the two streams are at room temperaturewhen combined in the process, lignin separates as a high water contentplastic mass which then can be dewatered by heating as previouslydisclosed. However, when the two liquids are mixed while heated to theelevated temperature, lignin solids precipitate to cause its dewateringupon cooling. The mixing can result from any form of mixing as known inthe processing arts, including mixing induced by physical means, e.g.,mixing blades, as well as process design to produce mixing by thecombining of flowing process streams. Such processing can be configuredas batch, continuous, or semi-continuous.

The lignin solids require a finite reaction time for theirtransformation to the dewatered (consolidated) state. This can beimplemented by discharging the combined flow—after mixing to producelignin precipitate—into a separating tank. The tank can be of any shapeor size that allows for the desired separation. In one aspect, theseparating tank is a conical bottomed tank. By introducing the combinedflow into a tank, the necessary time is provided for cooling andcompleting the lignin solids consolidation process and separating thedewatered solids by gravity into the bottom of the tank. Dewateredlignin solids can be removed from the process by any physical separationmeans. In one aspect, a screw conveyor or a similar suitable materialhandling device positioned to receive the solids flowing from bottom ofthe tank can be used to separate the dwatered lignin solids.

An example process for this is illustrated in FIG. 3. The black liquorfrom the paper mill, which emerges from the paper mill digestion/fiberseparation at temperatures in range of about 200° F. to about 300° F.,and in one aspect, about 200° F., is delivered, arrow 40, to blackliquor surge and mixing tank 42 where the black liquor is mixed withpolymer solution, line 44, from polymer solution day tank 46, and withclarified liquor for dilution, line 48, from clarified liquor tank 50.It has been found that a volume ratio of dilute black liquor, i.e.,black liquor as it is discharged directly from the digestion/fiberseparation, to clarified liquor of about 1:1 works well. Mixing rangesvary depending on material used and can range from about 5:1 to about1:5. Dilute black liquor, as used herein, is consistent with industryuse and refers to the black liquor from digestion processing and priorto evaporation. The clarified liquor is heated by heater 52 to atemperature above 180° F. so that the temperature of the black liquor,with added polymer and clarified liquor, remains above 180° F. The hotmixed black liquor is pumped by pump 54 to mixer 56 where the hot blackliquor with polymer therein is mixed with dilute phosphoric acid, line58, from acid tank 60, which has been heated by heated clarified liquoradded thereto, line 62. The pH of the combined streams should be acidicand, in one embodiment, is less than about pH 3.5. The volumetric ratioand/or pH of entering streams should be adjusted according. For example,one volume of dilute acid to three volumes of dilute black liquor is auseful volumetric ratio. The mixed black liquor is delivered to ligninseparation tank 64, e.g., a conical bottomed tank, where separation ofthe lignin from the black liquor occurs upon cooling. Time in ligninseparation tank 64 provides the necessary time for completing the ligninsolids consolidation process and the dewatered solids separate from theliquid by gravity into the bottom of the tank. Dewatered lignin solidscan be removed from the bottom of lignin separation tank 64 by a screwconveyor or a similar suitable material handling device positioned toreceive the solids flowing from bottom of the tank. The dewatered ligninsolids may be further processed by filtering, washing, and/or drying.

Experiments for the lignin consolidation process were carried out inbatch mode by heating the two liquids (black liquor and dilute acid) andmixing them while hot for successful consolidated formation of separatedand dewatered lignin solids. Dewatered lignin solids were separated fromthe liquor by filtration. Similar experiments of a continuous process ofheating the two liquids and mixing them have likewise been successful inresulting in separated dewatered lignin solids.

Whereas the invention is here illustrated and described with referenceto embodiments thereof presently contemplated as the best mode ofcarrying out the invention in actual practice, it is to be understoodthat various changes may be made in adapting the invention to differentembodiments without departing from the broader inventive conceptsdisclosed herein and comprehended by the claims that follow.

The invention claimed is:
 1. A method of at least partially dewateringlignin plastic solids in the form of a lignin plastic mass having amoisture content of more than about 60%, comprising: heating the ligninplastic mass to a temperature above a critical temperature; cooling theheated lignin plastic mass to a temperature below the criticaltemperature thus causing lignin plastic solids to agglomerate into lowermoisture granular lignin solids and a residual liquid, said lowermoisture granular lignin solids having a moisture content of less thanabout 60%; and separating at least a portion of the residual liquid fromthe lower moisture granular lignin solids to obtain dewatered granularlignin plastic solids.
 2. The method of claim 1, wherein the lowermoisture solids have a moisture content of less than about 50%.
 3. Themethod of claim 1, wherein the lower moisture granular lignin solidshave a moisture content of from about 45% to about 55%.
 4. The method ofclaim 1, wherein the critical temperature is greater than about 170° F.5. The method of claim 1, wherein the critical temperature is greaterthan about 180° F.
 6. The method of claim 1, wherein the criticaltemperature is from about 170° F. to about 200° F.
 7. A process fortreating a substantially spent, alkaline and non-sulphite digestionliquor obtained from digestion of a cellulosic biomass, said digestionliquor containing lignin as a potential precipitant upon acidificationof said digestion liquor, leaving substantially clarified residualliquid, said process comprising: mixing into said spent digestion liquora water soluble, surface active, polymeric, coagulant agent; acidifyingthe so mixed liquor to a pH below 7 to separate the lignin and otherorganic compounds and to coagulate them as solids which tend to float tothe surface of the residual liquid to form a lignin plastic mass havinga moisture content above about 60%; heating the lignin plastic mass to atemperature above a critical temperature; cooling the heated ligninplastic mass to a temperature below the critical temperature thuscausing the lignin plastic solids to agglomerate into lower moisturegranular lignin solids and a residual liquid, said lower moisturegranular lignin solids having a moisture content of less than about 60%;and separating at least a portion of the residual liquid from the lowermoisture granular lignin solids to obtain dewatered granular ligninsolids.
 8. The process of claim 7, wherein a surface active agentcoactive with the polymeric, coagulant agent is added to the spentdigestion liquor prior to the acidification thereof so as to coact withthe polymeric coagulant agent and thereby facilitate lignin separation.9. The process of claim 7, wherein the step of acidifying the so mixedliquor to a pH below 7 is the step of acidifying the so mixed liquor toa pH below 3.5.
 10. The process of claim 7, wherein the spent digestionliquor is taken from a pulping plant of the paper making industry. 11.The process of claim 7, wherein the spent digestion liquor is dilutedprior to treatment.
 12. The method of claim 7, wherein the dewateredgranular lignin solids have a moisture content of less than about 50%.13. The method of claim 7, wherein the dewatered granular lignin solidshave a moisture content of from about 45% to about 55%.
 14. The methodof claim 7, wherein the critical temperature is greater than about 170°F.
 15. The method of claim 7, wherein the critical temperature isgreater than about 180° F.
 16. The method of claim 7, wherein thecritical temperature is from about 170° F. to about 200° F.
 17. Themethod of claim 7, wherein the step of cooling the heated lignin plasticmass includes the step of placing the heated lignin plastic mass in atank, wherein the lower moisture granular lignin solids collect in thebottom of the tank, and the step of separating at least a portion of theresidual liquid from the lower moisture granular lignin solids includesremoving lower moisture granular lignin solids collected in the bottomof the tank from the tank.